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研究极端条件下固相分子晶体含能材料的相变机理，对于人们认识固相含能材料的爆轰反应有着重要的意义. 采用基于校正密度泛函理论的第一性原理方法研究固相硝基甲烷在静水压下的行为. 分析晶格参数a，b和c 轴随压强的变化，发现在1 GPa到12 GPa时晶格参数出现不连续的变化，表明体系发生相变. 在相变时最大的二面角从155.3°增加到177.5°，二面角的增加限制CH3官能团自由旋转，使得C–N和C–H键的键长发生变化. 在相变之前，体系主要存在由C–H…O组成的分子间的氢键，而在相变之后存在分子内的H…O和分子间C–H…O组成的氢键. 此外通过对硝基甲烷体系的电子结构进行计算，发现相变会影响带隙随压强的变化，而且还会影响费米能级附近的态密度结构.The solid phase transition in crystals prepared from molecular energetic materials under extreme conditions is important for understanding the detonation mechanisms. By applying the first principles density functional calculations, a detailed theoretical study of the lattice parameters and molecular structures, equations of state, densities of state for solid nitromethane is reported. By analyzing the pressure dependence of lattice parameters, a sudden change of the lattice parameters occurs between 10-12 GPa, implying that a transition has taken place. It is also found that the maximum dihedral angle of H-C-N-O has increased from 155.3° to 177.5°, indicating that a rotation of the methyl group from a staggered to an eclipsed conformation occurs in the pressure range 11–12 GPa. Before the phase transition, the intramolecular O … H–C interactions are mainly of hydrogen bonds. After the phase transition, the intramolecular and intermolecular O … H interactions are mainly of the hydrogen bonds. Phase transition also affects the reduced ratio of band gap and the density of state near the Fermi level.
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Keywords:
- phase transition /
- nitromethane /
- DFT-D
[1] Ou Y X 2006 Explosives (Beijing: Beijing Institute of Technology Press) p5 (in Chinese) [欧育湘 2006 炸药学(北京:北京理工大学出版社)第5页]
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[35] Vanderbilt D 1990 Phys. Rev. B 41 7892
[36] Clark S J, Segall M D, Pickard C J, Hasnip P J, Probert M I, Refson K, Payne M C 2005 Zeitschrift fr Kristallographie 220 567
[37] Murnaghan F D 1944 PNAS 30 244
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[40] Yarger F L, Olinger B 1986 J. Chem. Phys. 85 1534
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[42] Tkatchenko A, Scheffler M 2009 Phys. Rev. Lett. 102 073005
[43] Sorescu D C, Rice B M, Thompson D L 1999 J. Phys. Chem. A 103 989
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[1] Ou Y X 2006 Explosives (Beijing: Beijing Institute of Technology Press) p5 (in Chinese) [欧育湘 2006 炸药学(北京:北京理工大学出版社)第5页]
[2] Zhou T T, Huang FL 2012 Acta Phys. Sin. 61 246501 (in Chinese)[周婷婷, 黄风雷 2012 61 246501]
[3] Zhang B P, Zhang Q M, Huang F L 2009 Detonation Physics (Beijing: Weapon Industry Press) p140 (in Chinese) [张宝平, 张庆明, 黄风雷 2009 爆轰物理学(北京:兵器工业出版社)第140页]
[4] Trevino S F, Rymes W. H 1980 J. Chem. Phys. 73 3001
[5] Cromer D T, Ryan R R, Schiferl D 1985 J. Phys. Chem. 89 2315
[6] Courtecuisse S, Cansell F, Fabre D, Petitet J P 1995 J. Chem. Phys. 102 968
[7] Courtecuisse S, Cansell F, Fabre D, Petitet J P 1998 J. Chem. Phys. 108 7350
[8] Citroni M, Datchi F, Bini R, Di Vaira M, Pruzan P, Canny B, Schettino V 2008 J. Phys. Chem. B 112 1095
[9] Pinan Lucarré J, Ouillon R, Canny B, Pruzan P, Ranson P 2003 J. Raman. Spectrosc. 34 819
[10] Margetis D, Kaxiras E, Elstner M, Frauenhim Th, Manaa M R 2002 J. Chem. Phys. 117 788
[11] Reed E J, Jannopulos J D, Fried L E 2000 Phys. Rev. B 62 16500
[12] Liu H, Zhao J, Wei D, Gong Z 2006 J. Chem. Phys. 124 124501
[13] Sorescu D C, Rice B M, Thompson D L J 2000 Phys. Chem. B 104 8406
[14] Manaa M R, Reed E J, Fried L E, Galli G, Gygi F 2004 J. Chem. Phys. 120 10146
[15] Reed E J, Manaa M R, Fried L E, Glaesemann K R, Joannopoulos J D 2007 Nature Physics 4 72
[16] Xu J C, Zhao J J 2009 Acta Phys. Sin. 58 4144 (in Chinese)[徐京城, 赵纪军 2009 58 4144]
[17] Chang J, Lian P, Wei D, Chen X, Zhang Q, Gong Z 2010 Phys. Rev. Lett. 105 188302
[18] Zhang L, Chen L 2013 Acta Phys. Sin. 62 138201 (in Chinese) [张力, 陈朗 2013 62 138201]
[19] Byrd E F, Rice B M 2007 J. Phys. Chem. C 111 2787
[20] Conroy M W, Oleynik I I, Zybin S V, White C T 2008 Phys. Rev. B 77 94107
[21] Dion M, Rydberg H, Schröder E, Langreth D C, Lundqvist B I 2004 Phys. Rev. Lett. 92 246401
[22] Langreth D C, Lundqvist B I, Chakarova-Kack S D, Cooper V R, Dion M, Hyldgaard P, Kelkkanen A, Kleis J, Kong L Z, Li S, Moses P G, Murray E, Puzder A, Rydberg H, Schroder E, Thonhauser T 2009 J. Phys. : Condens. Matter 21 084203
[23] Lin I C, Coutinho-Neto M D, Felsenheimer C, von Lilienfeld O A, Tavernelli I, Rothlisberger U 2007 Phys. Rev. B 75 205131
[24] Tavernelli I, Lin I C, Rothlisberger U 2009 Phys. Rev. B 79 45106
[25] Grimme S 2006 J. Comput. Chem. 27 1787
[26] Neumann M A, Perrin M A 2005 J. Phys. Chem. B 109 15531
[27] Tkatchenko A, Scheffler M 2009 Phys. Rev. Lett. 102 073005
[28] Conroy M W, Budzevich M M, Lin Y, Oleynik I I, White C T 2009 Aip Conf. Proc. 1195 805
[29] Budzevich M M, Landerville A C, Conroy M W, Lin Y, Oleynik I I, White C T 2010 J. Appl. Phys. 107 113524
[30] Conroy M W, Oleynik I I, Zybin S V, White C T 2009 J. Phys. Chem. A 113 3610
[31] Sorescu D C, Rice B M 2010 J. Phys. Chem. C 114 6734
[32] Landerville A C, Conroy M W, Budzevich M M, Lin Y, White C T, Oleynik I I 2010 Appl. Phys. Lett. 97 251908
[33] Appalakondaiah S, Vaitheeswaran G, Lebègue S 2013 J. Chem. Phys. 138 184705
[34] Hamann D R, Schlter M, Chiang C 1979 Phys, Rev. Lett. 43 1494
[35] Vanderbilt D 1990 Phys. Rev. B 41 7892
[36] Clark S J, Segall M D, Pickard C J, Hasnip P J, Probert M I, Refson K, Payne M C 2005 Zeitschrift fr Kristallographie 220 567
[37] Murnaghan F D 1944 PNAS 30 244
[38] Olinger B, Halleck P M 1975 J. Chem. Phys. 62 94
[39] Olinger B, Halleck P M, Cady H H 1975 J. Chem. Phys. 62 4480
[40] Yarger F L, Olinger B 1986 J. Chem. Phys. 85 1534
[41] Ortmann F, Bechstedt F, Schmidt W G 2006 Phys. Rev. B 73 205101
[42] Tkatchenko A, Scheffler M 2009 Phys. Rev. Lett. 102 073005
[43] Sorescu D C, Rice B M, Thompson D L 1999 J. Phys. Chem. A 103 989
[44] Von Dreele R B 1995 High Pressure Res. 14 13
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